JP2006517247A - Ester mixtures based on branched chain alcohols and / or branched chain acids and their use as polymer additives - Google Patents

Abstract

The present invention relates to ester mixtures, their use as polymer additives, and polymer compositions comprising said ester mixtures.

Description

  The present invention relates to the use of ester mixtures and ester mixtures as polymer additives. Furthermore, the present invention relates to a polymer composition comprising the ester mixture.

Commercial fatty alcohols and fatty acids have very different structures depending on the raw materials or the manufacturing process. Linear saturated alcohols of chain length _C 8 _{-C 22,} after the natural fats and oils by hydrolysis or methanolysis (methanolysis), obtained by hydrogenation of the resulting acid or methyl ester. Long-chain linear saturated fatty alcohols _{(C 22} ~C ₄₀₎ is a naturally occurring wax such as beeswax and montan wax. Linear saturated fatty alcohols having a C ₆ -C ₂₀ chain length are obtained petrochemically by a Ziegler process using aluminum, hydrogen, and ethylene. Furthermore, a product having a chain length in the range of C _{20 to} C ₆₀ can be produced by converting an α-olefin obtained by ethylene polymerization into an alcohol and an acid (unilin alcohol and uniphosphoric acid).

  Semi-linear fatty alcohols, such as, for example, NEODOL ™ alcohol, can be synthesized by selective hydroformylation of the resulting α-olefin after ethylene oligomerization. Such alcohols (modified oxo alcohols, referred to as MO) contain approximately 80% primary, straight chain, and saturated alcohols. The residue mainly comprises alcohols that are alkyl-branched at the 2-position relative to the alcohol group.

  Conventional oxo alcohols (referred to as NO) are generally based on kerosene. Here, first a paraffin stream is isolated, after which it is dehydrogenated to olefins and finally hydroformylated. The fatty alcohol obtained thus contains approximately 50% primary, linear and saturated fatty alcohols. Almost all of the resulting branched alcohol is branched at the 2-position. Moreover, it is known that this product stream can be broken down into linear and branched components.

In addition to the majority of these fatty alcohols being monobranched, multi-branched fatty alcohols are also known. Such fatty alcohols are obtained by oligomerization and hydroformylation of propene and / or butene. Standard chain length of such alcohols, for example isononanol, isodecanol, and the like as in the isotridecanol (modified fatty alcohol) in the range of C ₆ -C _15. Acids corresponding to the alcohols described above are also known.

  In recent years, a new class of fatty alcohols has become accessible due to the hydroformylation of olefins obtained in a Fischer-Tropsch (FT) process using synthesis gas. Compared to known fatty alcohols, the latter fatty alcohols have special structural characteristics. For example, they may contain on average approximately 50% of branched molecules, like conventional oxoalcohols, but in contrast to prior art alcohols, the majority of those molecules are in the 2-position relative to the hydroxyl group. Not branched.

特に高分子添加物として適した新規なエステル混合物を提供することが本発明の目的である。加えて前記混合物は、高分子とよく適合し、直鎖アルコールに基づくエステルと比べると低い融解温度であるという利点に加えて、優れた放出特性を有するはずである。

It is an object of the present invention to provide a novel ester mixture which is particularly suitable as a polymer additive. In addition, the mixture should have excellent release characteristics in addition to the advantages of being well compatible with polymers and having a lower melting temperature compared to esters based on linear alcohols.

The novel ester mixture exhibiting surprising properties can be prepared from the alcohol and acid obtained in a Fischer-Tropsch process. The ester mixture is substantially
Consisting of an ester [KY1] having 1 to 4 carboxyl groups and 12 to 60 carbon atoms,
Optionally, one or more carboxylic acids that are fully or partially halogenated, and / or one or more phosphoric acids,
Adjusted by reaction with one or more alcohols,
The carboxylic acid, the alcohol, or both (but at least one) exists as a mixture, and the carboxylic acid mixture and / or the alcohol mixture is
It has an alcohol according to the chemical formula RCH ₂ OH and / or a carboxylic acid according to the chemical formula RCOOH,
(A) In 20% to 80% by weight, preferably 40% to 70% by weight, of the alcohol and / or acid used, the hydrocarbon radical R is linear and aliphatic, preferably saturated. And further having 4 to 20, preferably 7 to 12 carbon atoms, and (b) 10% to 80% by weight, preferably 20% by weight, of the alcohol and / or acid used. At ˜60% by weight, the hydrocarbon radical R is aliphatic, preferably saturated, and further has 4-20, preferably 7-12 carbon atoms, of which the upper limit is 3 Preferably, 1 or 2 are tertiary carbon atoms, and neither of the tertiary carbons is in the 2nd or 3rd position with respect to the —OH group of the alcohol or acid, and further in the mixture. At least 80%, most preferably at least 95% of the tertiary carbon atoms with respect to all tertiary carbon atoms are not directly adjacent, and further optionally
(C) up to 10% by weight, preferably up to 5% by weight of other alcohols or acids, which have 5 to 21, preferably 8 to 13 carbon atoms;
The alcohol, acid or both according to (a), (b) and (c) supplement each other up to 100% by weight.

  Preferred embodiments of the invention are presented in the dependent claims or are described below. The radical R preferably contains 11 to 12 carbon atoms on average, and each carbon atom preferably refers to the radical R. The ester mixture is a mixture of miscellaneous esters. The aforementioned weight percent refers to the composition of the ester mixture.

  The ester mixtures of the present invention are mono-, di-, tri-, and tetra acids or phosphoric acids and monoalcohols, or mono-, di-, tri-, and tetraalcohols and monocarboxylic acids. The carboxylic acid, the alcohol, or both are present as a mixture. When both are mixtures, they are the reaction product of a monoalcohol and a monocarboxylic acid.

  As used herein, the term “polymer additive” refers to, for example, plasticizers, lubricants, mold release agents, viscosity reducing agents, antioxidants, solvents, and the like. Their utility depends on both the ester structure and the polymer type.

With respect to the phthalates according to the invention, they are particularly useful as plasticizer PVC, with a compatibility limit averaging about 13 carbon atoms in the alcohol residue. For example, a commonly known plasticizer is diisotridecyl phthalate (DTDP), but there are also plasticizers based on C ₁₂ -C ₁₃ alcohol mixtures.

Since the compatibility of long chain alcohol residues is so limited, in the technique for using alcohol mixtures, long chain alcohols of C ₁₂ and / or C ₁₃ are converted to short chain alcohols ( It has been proposed to mix with an ester mixture). Despite the excellent compatibility of prior art ester / plasticizer mixtures, their heat aging stability is not satisfactory when compared to the esters of the present invention. The fatty alcohols obtained in the FT synthesis are particularly suitable for the preparation of polymer-added esters, especially for use as plasticizers, most preferably for PVC.

Preferably, the alcohol of the ester has a chain length of _C 5 _{-C 15,} preferably _C 8 _{-C 13,} most preferably _C 12 _{-C 13.} The acid may be an aliphatic, cyclic, and / or aromatic acid. Examples of the aliphatic acid include formic acid, acetic acid, propanoic acid, butyric acid, isobutyric acid, pentanoic acid, caproic acid, heptanoic acid, caprylic acid, peragonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid , Eicosanoic acid, tallow fatty acid, coconut fatty acid, coconut fatty acid, ricinoleic acid, oleic acid, linoleic acid, linolenic acid, behenyl fatty acid, isostearic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, 2-ethylhexanoic acid, 2-propylheptane Acid, 2-butyloctanoic acid, 2-butyldecanoic acid, 2-hexyloctanoic acid, 2-hexyldecanoic acid, 2-hexyldecanoic acid, 2-octyldecanoic acid, 2-octyldodecanoic acid, 2-decyltetradecanoic acid, 2- Dodecyl hexadecanoic acid, 2-tetradecyl octadecanoic acid Benzoic acid, cyclohexanecarboxylic acid, glycolic acid, lactic acid, hydroxybutyric acid, mandelic acid, glycerol acid, acrylic acid, such as methacrylic acid, a branched or straight-chain, mono- saturated or unsaturated C ₂ -C ₂₂ It may be a carboxylic acid or, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid It may be a di-, tri-, or tetracarboxylic acid such as acid, malic acid, tartaric acid, 1,2-cyclohexanedicarboxylic acid, trimellitic acid, citric acid, pyromellitic acid, or tetrachlorophthalic acid.

Furthermore, the present invention is _C 5 _{-C 15,} preferably _C 8 _{-C 13,} and most preferably is associated with esters based on acids having a chain length of _C 12 _{-C 13,} for example, aliphatic or cyclic or aromatic Including branched or straight chain acids such as ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, Octadecanol, eicosanol, tallow fatty alcohol, coconut fatty alcohol, coconut fatty alcohol, castor oil alcohol, oleyl alcohol, linoleic alcohol, linolenic alcohol, behenyl alcohol, isostearyl alcohol, isooctanol, isononona Nord, isodecanol, 2-ethylhexane alcohol, 2-propylheptanol, 2-butyloctanol, 2-butyldecanol, 2-hexyloctanol, 2-hexyldecanol, 2-hexyldecanol, 2-octyldecanol, 2- Octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, 2-tetradecyloctadecanol, benzyl alcohol, cyclohexanol, vinyl alcohol, lactic acid, hydroxylbutyric acid, mandelic acid, glycerol acid, citric acid, phenol , monoalcohols or such as ethylene glycol, of C ₂ -C ₂₂ saturated or unsaturated, such as, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, Penchire Di- such as glycol, hexylene glycol, neopentyl glycol, malic acid, tartaric acid, cyclohexanediol or glycerol, trimethylolpropane or alditols, diglycerides, triglycerides, polyglycerides, pentaerythritol or dipentaerythritol , Tri-, or poly-alcohols.

  Examples of the ester include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylate (for example, polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA)), and fluorinated polymer (for example, fluorinated). Polyvinylidene (PVDF), polytetrafluoroethylene (PTFE)), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetal (eg, polyvinyl butyral (PVB)), polystyrene polymer (eg, polystyrene (PS), expandable polystyrene) (EPS), acrylonitrile-styrene-acrylate (ASA), styrene acrylonitrile (SAN), acrylonitrile-butanediene-styrene (ABS), styrene-maleic anhydride Polymer (SMA), styrene methacrylic acid copolymer), polyolefin (for example, polyethylene (PE), polypropylene (PP), thermoplastic polyolefin (TPO), polyethylene vinyl acetate (EVA), polycarbonate (PC), polyethylene terephthalic acid ( PETP), polybutylene terephthalic acid (PBTP), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPO), biopolymer (eg, polylactic acid (PLA) ), Polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV)), polyester, starch, cellulose and cellulose derivatives (eg nitrocellulose (NC), ethylcellulose (EC), cellulose acetate Scan (CA), acetate / butyrate (CAB)), silicone, and mixtures of the above polymers or copolymers, or the like thereof monomer units, are useful as additives for various polymer.

  The esters are particularly suitable for PVC plasticizers. The average molecular weight of PVC is defined as the k value and is measured according to DIN 53726. The standard k value is in the range of 60-100, i.e. the average molecular weight (average viscosity) is in the range of approximately 60,000-150,000 g / mol. Besides the molecular weight, the processing properties of PVC are also influenced by the production method. Suspension PVC (S-PVC), emulsion PVC (E-PVC), and bulk PVC are distinguished, with S-PVC and E-PVC being the most common.

  A wide range of additives include polymeric plastics, primary plasticizers, and stabilizers such as heat stabilizers, light stabilizers, antioxidants, biostabilizers, as well as fillers, lubricants, mold release agents, It can also be added to foaming agents, flame retardants, extenders, secondary plasticizers, pigments and dyes, antistatic agents, processing aids, and impact polymerization modifiers.

  Plasticizers are usually esters such as phthalic acids, trimellitates, citrates, adipates, sebacates, polyesters, sulfonates, phosphate esters, benzoates, glycerides, rarely Pyromellitates and polyol esters. A heat stabilizer generally means a metal soap. Here, for example, single metal stabilizers such as tin and lead stabilizers, and mixed metal stabilizers such as cadmium-copper stabilizers, barium-copper stabilizers, calcium-copper stabilizers, and A distinction is made between metal-free organic stabilizers such as aminocrotonates, epoxidized soybean oil, phosphites, epoxy resins, α-diketones and the like. Antioxidants generally mean sterically hindered phenols, thioesters, phosphites, and amines. Commonly used extenders or secondary plasticizers are, for example, hydrocarbons, chlorinated paraffins, epoxidized soybean oil, and TXIB (2,2,4-trimethylpentane-1,3-diol diisobutyrate). Common fillers are, for example, calcium carbonate, kaolin, carbon black, talc powder, dolomite, silicates and aluminates.

  Regarding lubricants, a distinction is made between internal and external, and the boundary between the two groups is liquid. The lubricants used are usually eg isobutyl stearate, distearyl phthalate, glycerol monoolate (GMO), glycerol monostearate (GMS), di- and triglycerol fatty acid esters, stearyl stearate Esters such as salts, complex esters, fatty alcohols, fatty acids, soaps, amide waxes, oxidized and non-oxidized polyethylene waxes, and paraffins. Common blowing agents are primary chemicals such as azobisisobutyronitrile, troylsulfohydrazide and the like. Flame retardants are phosphates, antimony trioxide, aluminum hydroxide, magnesium hydroxide, chlorinated hydrocarbons, and borates. Currently available stabilizers are primarily multi-component systems that further include thermal stabilizers, antioxidants, light stabilizers, lubricants, and liquefiers, and include (secondary) plasticizers.

  S-PVC is generally processed using a dry mixing method, while E-PVC is processed as a paste. Here, a conventional mixture is used in the first stage. The paste is then processed, for example, by a coating technique or rotary integral molding. The dry mixture is usually extruded and then calendered. Other conventional methods include extrusion molding, inflation processes, slush molding, and techniques for processing other thermoplastic materials.

  The term “phr” as used in the formulation means a value for 100 parts of polymer resin per weight. The formulation contains 1-150 phr plasticizer, 0.5-10 phr stabilizer, 0-50 phr filler, and other additives as required.

  The structure of the FT fatty alcohol has proved particularly suitable with regard to the preparation of the PVC plasticizer, i.e. the polymer compatibility and the mechanical properties of the resulting plastic sheet. Further, the ester has a more preferable melting temperature compared to an ester plasticizer based on a linear alcohol so that it can be easily treated.

The above description will be explained using phthalate as an example. Esters based on various alcohols of C _12/13 were _prepared for comparison, conventional oxo alcohols (NO type, SASOL LIAL ™ 123), modified oxo alcohols (MO type, Shell's NEODOL ™ 23) , And phthalate esters based on FT oxoalcohol (FT type, SASOL ™ 23 from SASOL, according to the present invention) were compared to each other. The state-of-the-art technology is, for example, di (decyl, lauryl, myristyl) phthalate (LINPLAST ™ 1012 BP), di (octyl, decyl) phthalate (LINPLAST ™ 810 P), and diisotridecyl phthalate Indicated by high performance phthalate plasticizers such as acid esters (LINPLAST ™ 13 XP).

  When the esters are compared, it is clear that their melting points are gradually decreasing, that is, from MO phthalates to FT phthalates and NO phthalates. With respect to the melting point / casting temperature (clearing point), the FT phthalate exhibits a surprisingly similar reaction to the branched alcohol phthalate.

  Comparing the gelation temperatures of the various plasticizers, it is clear that FT oxo alcohol is most suitable for adjusting the plasticizer. The gelling temperature is also a measure of the polymer compatibility of the plasticizer and is significantly lower than the temperatures of MO- and NO phthalates, the latter exhibiting the most undesirable gelling behavior.

When the mechanical properties of the sheets containing various plasticizers are compared, there is no significant difference. However, as inferred from the gelation temperature, it is clear that the plasticizer based on FT oxo alcohol is excellent in compatibility. MO phthalate and NO phthalate leached considerably from 33% standard plastic sheets, whereas phthalates based on FT C _12/13 alcohols have only minor incompatibility with such sheets I know.

However, when preparing a phthalate ester plasticizer based on a 70:30 mixture of a C _12/13 alcohol and a linear C _8-14 alcohol such as, for example, LINCOL ™ 812 H, the plastic containing FT oxo alcohol The agent is perfectly compatible when compared to products containing conventional oxo alcohols. Unlike the prior art products, there is no significant degradation of the plasticizer volatility.

Thus, plasticizers based on FT alcohols have very low release (eg spraying, degradation due to aging, etc.) during periods when their compatibility is sufficient. This is also demonstrated, for example, by cable formulations. In formulations containing such fillers, no incompatibility of phthalate esters based on C _12/13 FT oxo alcohols has been observed.

Prior art phthalates based on oxo alcohols made from tributene (diisotridecyl phthalate) have excellent heat aging stability. However, the thermal aging stability of phthalates based on C _12/13 FT oxo alcohols is considerably better than the aforementioned diisotridecyl phthalates. Even the heat aging stability of phthalate plasticizers based on 70:30 mixtures of C _12/13 alcohols and linear C _8-14 alcohols such as, for example, LINCOL ™ 812 H, said diisotridecyl phthalic acid Inferior to esters.

In addition, another advantage of phthalates based on C _12/13 FT oxo alcohols is excellent low temperature flexibility, which can be demonstrated, for example, by the Crash & Berg torsional load test. This test shows that despite the slight increase in the initial hardness of the sheet (compared to 100%), a phthalate ester based on C _12/13 FT oxoalcohol, for example LINPLAST® from SASOL Germany GmbH ) Evidence that it exhibits good low temperature properties as well as the prior art phthalates based on linear C _10-14 alcohols such as 1012 BP. Thus, phthalates based on C _12/13 FT oxo alcohols are clearly superior to diisotridecyl phthalates. The same applies to esters based on mixtures containing, for example, linear alcohols and FT oxo alcohols.

  In addition, plastic sheets containing phthalate esters based on FT oxo alcohols have high thermal stability (Congo), as well as sheets containing phthalate esters based entirely on linear alcohols such as LINPLAST ™ 1012 BP. Red test). Such plasticizers therefore have unique practical advantages over conventional diisotridecyl phthalate esters. Thus, plasticizers based on FT oxo alcohols are clearly superior to prior art plasticizers.

Charged SASOL of LINPLAST (TM) 13 XP (diisotridecyl phthalate), LINPLAST (TM) 1012 BP (di _{(C 10 to 14} alkyl) phthalate), LIAL _{(TM) 123 (C 12 to 13} oxoalcohols ), SAFOL ™ 23 (C ₁₂ -C ₁₃ FT oxo alcohol), LINCOL ™ 810 (octanol / decanol mixture), LINCOL ™ 812 H (octanol / decanol / dodecanol / tetradecanol mixture).
Shell's NEODOL ™ 23 (modified C ₁₂ / C ₁₃ oxo alcohol).
Chemson's NAFTOVIN ™ T80 (lead phthalate).
IRGASTAB (TM) BZ 561 (liquid barium / zinc stabilizer) from Cromton Vinyl Additives.

Preparation of ester preparation SAFOL ™ 23 phthalate ester 4.4 mol C _12/13 FT alcohol (SAFOL ™ 23) and 2.0 mol phthalic anhydride, 0.15 wt% tetraisopropyl titanate ester , And 150 ml of toluene with water separation and reflux for 6 hours. This temperature was raised to 180-210 ° C. By the end of the water separation, most of the entrained reagents were distilled off. After cooling, the excess alcohol was separated with a 0.3 mbar molecular evaporator and the outer temperature was 145 ° C.

Comparative Example 1 Preparation of NEODOL ™ 23 phthalate ester 3.45 mol C _12/13 modified oxo alcohol (NEODOL ™ 23) and 1.57 mol phthalic anhydride, 0.15 wt% tetraisopropyl The titanate ester and 150 ml of xylene were heated for 5 hours with water separation and reflux. This temperature was raised to 160 ° C to 180 ° C. By the end of the water separation, most of the entrained reagents were distilled off. After cooling, the excess alcohol was separated with a 0.13 mbar molecular evaporator, and the external temperature was 135 ° C.

Comparative Example 2 Preparation of LIAL ™ (123) phthalate ester 8.8 mol C _12/13 oxo alcohol (LIAL ™ 123) and 4.0 mol phthalic anhydride, 0.15 wt% tetra Isopropyl titanate and 150 ml of cyclohexane were heated for 5.5 hours with water separation and reflux. This temperature was raised to 160 ° C to 190 ° C. By the end of the water separation, most of the entrained reagents were distilled off. After cooling, the excess alcohol was separated with a 0.06 mbar molecular evaporator, and the external temperature was 140 ° C.

Preparation of SAFOL ™ 23 / LINCOL ™ 812 H phthalate ester 70 of C _12/13 FT alcohol (SAFOL ™ 23) and C ₈ -C ₁₄ linear alcohol (LINCOL ™ 812 H): 30 mixtures 9.9 mol, and 4.5 mol phthalic anhydride, 0.15 wt% tetraisopropyltitanium ester, and 150 ml cyclohexane were heated for 2.5 hours with water separation reflux. This temperature was raised to 160 ° C to 190 ° C. By the end of the water separation, most of the entrained reagents were distilled off. After cooling, the excess alcohol was separated with a 0.3 mbar molecular evaporator, and the exterior temperature was 115 ° C.

Comparative Example 3
Preparation of LIAL ™ 123 / LINCOL ™ 812 H phthalate 70 of C _12/13 oxo alcohol (LIAL ™ 123) and C _{8 to} C ₁₄ linear alcohol (LINCOL ™ 812 H): 30 mixtures 8.8 mol, and 4.0 mol phthalic anhydride, 0.15 wt% tetraisopropyl titanate, and 150 ml cyclohexane were heated with water separation reflux for 5.5 hours. This temperature was raised to 160-220 ° C. By the end of the water separation, most of the entrained reagents were distilled off. After cooling, the excess alcohol was separated with a 0.04 mbar molecular evaporator and the outer temperature was 140 ° C.

Preparation of SAFOL ™ 23 / LINCOL ™ 810 phthalate ester 50:50 mixture of C _12/13 FT alcohol (SAFOL ™ 23) and C ₈ -C ₁₀ linear alcohol (LINCOL ™ 810) 8.8 mol and 4.0 mol of phthalic anhydride, 0.15 wt% tetraisopropyl titanate, and 150 ml of xylene were heated for 7 hours with water separation and reflux. This temperature was raised to 170 ° C to 190 ° C. By the end of the water separation, most of the entrained reagents were distilled off. After cooling, the excess alcohol was separated with a 0.3 mbar molecular evaporator, and the exterior temperature was 125 ° C.

Synthesis of SAFOL23 acid 1950 g (10 mol) of SAFOL23 alcohol was heated to 335 ° C. with 730 g (13 mol) of potassium hydroxide. Hydrogen evolution ended in 4 hours. The resulting potassium soap was cooled to ambient temperature and neutralized by adding excess sulfuric acid. After phase separation, the organic layer was washed several times with water until the aqueous phase became a neutral reaction.

Preparation of pentaerythritol tetrakis (SAFOL23 acid) ester 1500 g (7.2 mol), 220 g (1.6 mol) of pentaerythritol, 200 ml of xylene, and 2. ml of the reaction product of Example 1 (SAFOL23 acid). 6 g (0.15 wt% tetraisopropyl titanate ester was heated in a flask to 180 ° C. At this temperature, separation of the water of reaction began. This heating was continued to increase to 240 ° C. The reaction The hydroxyl number was determined by GC analysis and calculated as 4.3 mg KOH per gram Excess acid and residual solvent were distilled off by short-stage distillation at 140 ° C. and 0.05 mbar. Pentaerythritol tetrakis (SAFOL23 acid) ester is isolated as a distillation residue, Was 55 Hazen color with an acid value of 0.15mg KOH per g.

Use of Pentaerythritol Tetrakis (SAFOL23 Acid) Ester as PVC Lubricant A PVC test sheet was prepared based on the following formulation.

100 phr PVC (K70)
50 phr plasticizer LINPLAST 610 P
(Di (hexyl, octyl, decyl) phthalate)
1.5 phr liquid barium / zinc stabilizer (IRGASTAB BZ 561)
0.3 phr lubricant (ester of Example 2)
The ingredients were mixed together, converted to a biaxial Brabender plastic coder and kneaded at 170 ° C. for 10 minutes. The torque curve showed strong signs that the pentaerythritol tetrakis (SAFOL23 acid) ester worked as an internal PVC lubricant. The pre-gelled PVC compound (called doll) was easy to remove from the shaft. No discoloration was observed. Thereafter, the compound was calendered on a two-roll calender for approximately 3 minutes to make the PVC foil 0.5 mm thick. Again, there was no discoloration and no volatilization or fuming was observed.

Internal (in-house) test method used to test the method DIN and ISO standards and testing of an ester and plastic sheet in accordance with Table 4.

Adjustment of plastic sheet (in-house test method 62-HF-1, analogy from DIN 7749, sheet 2)
The components of formulation 1 or formulation 2 described above were placed in a magnetic bottle and mixed together until a dry powder (dry mixture) was obtained. The powder was placed in a kneader (Brabender Plasti Corder), 170 ° C., 30 r. p. m for 10 minutes. The prepared compound was removed after aeration on a roll at 170 ° C. for approximately 3 minutes. The resulting sheet is then subjected to 3 steps using a hydroforming press (Polystat 200S): 1 minute at 170 ° C./70 bar, 3 minutes at 170 ° C./200 bar, and cooling from 170 ° C. to 100 ° C. at 200 bar 3 Extruded in the process. Thereafter, when the 33% PVC flexible sheet was extruded to a thickness of 0.5 mm, the cable sheet was 2 mm thick.

Melting point measurement (in-house test method 61-EE-9)
Approximately 50 ml of test compound was placed in a pour point beaker. A pour point thermometer was pierced into the sample at a depth of approximately 3 cm. The beaker was then placed in a cold mat cooling bath. The coolant temperature was gradually lowered until the sample became solid. Thereafter, the temperature of the cooling bath was further lowered to at least 4 ° C., and then the temperature was slowly raised approximately 2 degrees every 4 hours. The melting range was defined as the temperature between the start of melting and completion of melting.

Solution temperature measurement (in-house test method 61-EE-1)
2.5 mg S-PVC K70 in a 50 ml beaker was suspended in 47.5 mg plasticizer. This temperature was slowly increased (about 1 ° C. per minute). The solution temperature was defined as the temperature at which S-PVC was dissolved in the plasticizer and Arial 12 type letters were clearly visible through the solution.

Claims (11)

An ester mixture,
Substantially having an ester containing 1-4 carboxyl groups and 12-60 carbon atoms,
Said esters are optionally obtained by reaction of one or more alcohols with one or more carboxylic acids and / or one or more phosphoric acids which are totally or partially halogenated,
The carboxylic acid, the alcohol, or both are present as a mixture, the carboxylic acid mixture and / or the alcohol mixture comprising an alcohol according to the formula RCH ₂ OH and / or a carboxylic acid according to the formula RCOOH. Including the mixture,
(A) an acid using an aliphatic linear hydrocarbon radical R containing 20 to 80% by weight of alcohol and / or 4 to 20 carbon atoms;
(B) 10% to 80% by weight of an alcohol and / or an acid which is an aliphatic and hydrocarbon radical R containing 4 to 20 carbon atoms, and the carbon atom has a maximum of 3 tertiary carbon atoms. And an acid in which all the carbon atoms are not located at the 2- or 3-position of the —OH group of the alcohol or acid, and optionally (c) having 5 to 21 carbon atoms up to 10% by weight With other alcohols or acids,
The ester mixture, wherein the alcohol, the acid, or both, supplement each other to 100 wt% according to (a), (b), and (c).   In the ester mixture according to claim 1, 70% or more, preferably 80% or more, of the alkyl branch of the mixture is a methyl group and / or ethyl group, preferably a methyl group. In the ester mixture according to any one of the preceding claims, 80% or more, preferably 95% or more of the radical R of the mixture is —CH ₂ —OH group or —CH ₂ — linked to a —COOH group. those having a group - CH _2.   In the ester mixture of any one of the preceding claims, each radical R contains on average 0.1 to 2 tertiary carbon atoms, preferably 0.2 to 0.7. The ester mixture according to any one of claims 1 to 4, wherein the alcohol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, neopentyl glycol, malic acid, tartaric acid. 1 selected from the group consisting of: cyclohexanediol, glycerol, trimethylolpropane or alditol, diglyceride, triglyceride, polyglyceride, pentaeritol, dipentaerythritol, and C ₆ -C ₂₂ mono- or diol. One alcohol or a plurality of alcohols. 5. The ester mixture according to claim 1, wherein the mono-, di-, tri- and / or tetracarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid. , suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, malic acid, tartaric acid, cyclohexanedicarboxylic acid, trimellitic acid, citric acid, pyromellitic acid, and mono C ₆ -C ₂₂ - is selected from or dicarboxylic acids One carboxylic acid or a plurality of carboxylic acids.   5. The ester mixture according to claim 1, wherein the mono-, di-, tri- and / or tetracarboxylic acid is phthalic acid, isophthalic acid and / or terephthalic acid, or their tetrachloro substitution. Is a derivative.   A polymer mixture comprising the ester of any one of the preceding claims, and a polymer having a molecular weight greater than 500 g / mol.   10. Polymer mixture comprising the ester according to any one of claims 1 to 9, wherein the ester is 1 to 150 phr, preferably 20 to 100 phr, most preferably 30 to 60 phr.   10. Polymer mixture according to any one of claims 8 or 9, wherein the polymer is preferably PVC or the plasticizer comprising as a polymer PVC having a k value of 60-100 according to DIN 53 726.   Use of the ester mixture according to any one of claims 1 to 9 as a plasticizer, lubricant, mold release agent, flame retardant, extender for polymers having a molecular weight of more than 500 g / mol, in particular 20,000 Use, wherein the polymer is preferably PVC or comprises PVC.